Process for treating waste liquor.



E. H. WRIGHT 6I J. F. OAKLEAF,

PROCESS FOR TREATING WASTE LIQUOR,

APPLICATION FILED IuIIIiII. 19u.

Waste Liquor, of which the following is a U T i IGHT AND-TMES F. 'AKLEAE 0F CLEAN, NEW YORK, ASSIGNORS T0 VACUUM OIL COMIEANY, OF ROCHESTElB', NEW YORK, A CORPORATION OF NEW YORK.

rnocnss ron maremma- WASTE Lieven..

p -n n-c Speccation of Letters Patent.

neaaosi..

application med June ii, 191e serial no. 844,523.

To all 'whom t may'conbcm."

'.Be'i vknown thatwe, EDWARD H. Winona?. and Jaime F.- OAKLEAF, citizens of the United States, and residents of Olean, in the county of Cattaraugus and State of New York, have-invented certain new and useful Improvements in Processes for Treating specification. v

This invention relates to the treatment of 'waste-liquors containing mineral oil, parvticularly when the oil, or a part of it, is

mechamcally suspended, in a colloidal or finely-divided form, 1n a large volume of .Water which also contains soluble organic or mineralts- In. the manufacture of lubricating-oils from petroleum ,it is common to employ a decolorizing process which involves treatmeint of the oil with sulfuric acid, the oil `being afterward washed with. water to remove the acid and the salts produced thereby, -and the use of caustic soda to neutralize any residual acid, with further washing of the oil to remove the alkaline compounds which are formed by the soda, All of the water and the waste-products of this process are commonly mingled and discharged as Worthless, owing to the comparatively small amount of hydrocarbons contained thereby.

Y The discharge of waste liquors of the chari acter above described into water-courses 1s objectionable, as the dissolved substances vare destructive to fish and render the water imputable. Furthermore, we have discovered that the amountof solids and hydrocarbone recoverable Vfrom such liquors is' suiicient to-more than pay for the expense of their separation. Accordingly, the object of the present invention` is-to produce a process .whereby waste liquor of the kind in question may ,be treated' economically in such a manner as -to separate substantially all of the suspended and dissolved substances from the Water, and to convert the material so separated into lluids and solids of commercial value.

The process by which we attain the forcgoing object is based upon the fact that by treatment of the oil-containing waste liquor with a reagent, such as lime,. capable of forming, with the soluble salts, an insoluble precipitate, not only will the dissolved substances be vseparated from the water, but

'oil which is merely suspended therein, in c0lloidal or emulsied form, will also. be seplPatented Aug. 7, i917.

arated, owing to the fact that it is occluded by the precipitate, so that practically all of the foreign substances, may be collected Vin the form of a sludge of either greater or lesser specific gravity than that of the water,

sludge the water is substantially purified,

while at the same timel the oils. and solids are suliiciently concentrated to permit the economical recovery of the valuable constituents by distillation, which constitutes the inal 'step of our novel process. In this Y distillation the water' and the lighter Auncombined oils first pass od and may be con# densed and separated inthe usual manner. The temperature of the vstill is then raised .'suciently to evaporate-the heavier Oils and to decompose the salts of complex' sulfonic and sulfuric acids, thus producing further valuable distillates. .the operation there remains in the still a coke.- like residue which contains the inorganic acid and basicconstituents of the liquor, but which consists tlargely or chiefly of uncom- ,bined carbon, so that the residue has a substantial fuelvalue The process above described may be carried out in any well-known apparatus for conducting the several essential steps. In the accompanying drawing, however, we have shown, diagrammatically, an arrange- Vment of apparatus suitable for the purpose.

In the illustrated apparatus the oillcontaining liquor -is pumped, through a pipe 1,V

into a large receptacle 2, which may be described as an agitator, in which the -precipitating operationis carried out. In this agitator the reagent such, for example, as milk of lime, is added to the liquor through a pipe 3. A

' rIhe reaction in the agitator is facilitated by agitating .its contents by the injection of compressed air at the bottom of the agitator, and for this purpose we have'sliown acornpresser which supplies air to the agitator through a valve-controlled pipe Assuming that the waste liquor to be treated is the ordinary 'waste from the acid and alkali process of decoiorizingvoil, its

At the termination of l Vin which the distillate constituents, besides a large volume of Water, usually' comprise finely-divided uncom- -bined oil in colloidal or emulsied form,

sodium salts of sulfonic acid, sodium salts ofcompound sulfuric acids, and small quantities of free acid or tarry substances. When this mixture is agitated with the milk of lime insoluble calcium salts are formed, by the reaction of the lime with all of the dissolved substances in the sewage, so that practically all of the solids are separated in the form of an insoluble precipitate. At the same time practically all of the uncombined oil suspended in the Water is occluded by this precipitate. When the agitation has been continued suiliciently to' complete the reaction the introduction of air is stopped, and the contents of the agitator are then allowed to stand long enough for .the precipitate and the occluded oil to separate, by the action of gravity, in the form of a sludge, which may either settle or float, according to the character of its contents.

The sludge at the bottom of the agitator is next drawn off through a valve-controlled pipe 5, which discharges into a receptacle or sump 6, and next the supernatant cleaxr Water is drawn oil' through a valve-controlled pipe 7, after which such of the sludge as floated at the top is drawn into the sump.

he clear water is substantially purified, except that in some cases a small quantity of the most liocculent parts of the precipitate may remain in it. For the removal of such matter it is passed through a sand-filter 8, but in most cases it may be passed directly through a by-pass pipe 9, and discharged at any convenient point, such as a running stream, in a purified and harmless condition.

The sludge which is collected in the sump -6 is next pumped, through a pipe 10, into a Storage-tank 11 from which it may be drawn in successive charges, through a pipe 12, into the still 13. This still is first-heatedl water remaining.

sulliciently to vaporize the in the sludge, together with the lighter uncombined hydrocarbons or oils, and the distillate is passed through a condenser 15, the eflluent from which passes through a lookfbox 16 to valves 17, by which it may bedirected 4selectively to tanks 18 and 19, is collected and the oil is permitted to separate from the water. After the evaporation of the water and the lighter oils, the temperature of the still is raised sufficiently to vaporize the heavier oils, a temperature of approximately-700 being necessary Vfor the heaviest petroleum constituents, and at the same time the oil-containing calcium compounds are decomposed, the hydrocarbons being thus be removed The final residue in the still, containing the inorganic bases, and acids, and also a large quantit of uncombined carbon, may

rom the still through a manhole 20 and used economically as fuel, for the purpose of heating the still, or for any other purpose.

Although we have shown only a single agitator and still, it is preferable, for the sake of continuous operation, to employ bat,

teries of these devices which can be used alternately'.

While we have described our novel process particularlyv as applied to waste liquor resulting from the acid and alkali process for decolorizing oil, it will be apparent that it is applicable to any waste liquor containing oil, together with a suilicient quantity of soluble salts to permit the formation of a precipitate which will collect the oil mechanically suspended in the liquor, and it will` also be apparent that where the amount of such soluble substances is not suliicient for this purpose it may be augmented by the addition ofsuitable salts, in addition to the lime or other precipitating reagent.

We claim 1. The rocess of oil-recovery which comprises (1) the treatment of waste liquor from the acid and alkali treatment of min- 'eral oil consisting Vchiefly of water, containing salts including complex sodium sulfonates and sodium sulfates in solution and a relatively small quantity of oil suspended in finely divided form, with a reagent capable of producing, with the said soluble salts, an insoluble precipitate in which the suspended oil is occluded; and (2) the mechanical separation of the bulk of the clarified water from the resulting precipitate.

2. The rocess of oil-recovery which comprises (1)) the treatment of waste liquor from the acid and alkali treatment of mineral oil consisting chiefly of water, containing salts including complex sodium sulfonates and sodium sulfates in solution and a relatively small quantity of oil suspended in finely divided form, with a reagent capable of producing, with the said soluble salts, an insoluble precipitate in which the suspended oil is occluded; (2) the mechanical separation of the bulk of the clarified water from the resulting precipitate; and (3) the dry ing and distillation of the sludge to recover the oil therefrom.

3. The rocess of oil-recovery which comprises (ll) the treatment of waste liquor from the acid and alkali treatment of mineral oil consisting chiefly of water, contain ing salts including complex sodium sulfonates and sodium sulfates in solutionand a relatively small quantity of oil suspended in finely divided form, with a rea ent capable of producing, with the said soliile salts, an insoluble precipitate in which the suspended i oil is occluded; (2) the mechanial separaa coke-like body comprising fiee carbon/aria -ton of the bulk f the clarified water'from mineral salts. theresulting prepipitatej (3) the evapora- EDWARD H. WRIGHT.

tion of the remalmng water from the pre- JS F. QAKLEAF. 5 cipitate; and (4)' the destructive distillation Witnesses:

f the dried sludge to recover hydroeubons HG1-:ORGE A. N

there'om, therebyredcing the residuum te JAms E. FANE. 

